利用活性酵母细胞催化4-氯乙酰乙酸乙酯(COBE)的不对称还原可以直接合成具有光学活性的4-氯-3-羟基丁酸乙酯(CHBE).实验发现,在水相体系中主要生成D-(S)-型产物,COBE的转化率及CHBE的收率和光学选择性都比较高.考察了底物和产物的浓度、辅助底物的种类和浓度、系的pH和温度以及菌体培养条件等因素对反应的影响.结果表明,在较低COBE浓度下R型产物占优,在高浓度下主要是S型产物;较高的反应温度有利于S型产物的生成,pH≈8.0时可获得较高的S型产物选择性;产物CHBE对COBE的还原反应具有一定的抑制作用.在酵母催化COBE还原的同时需要一定的辅助底物来再生辅酶NAD(P)H,利用乙醇、异丙醇和仲丁醇作辅助底物可获得较高的立体选择性.对数生长期和厌氧条件培养的细胞对生成S型产物较有利.
参考文献
| [1] | Rouhi A M .[J].Chemical and Engineering News,2003,81(18):45. |
| [2] | Servi S.[J].Synthesis-Stuttgart,1990(1/2):1. |
| [3] | Yang F;Russell A J .[J].Biotechnology Progress,1993,9(03):234. |
| [4] | Marino JP.;McClure MS.;Holub DP.;Comasseto JV.;Tucci FC. .Stereocontrolled synthesis of (-)-macrolactin A[J].Journal of the American Chemical Society,2002(8):1664-1668. |
| [5] | Song C E;Lee J K;Lee S H;Lee S-G .[J].Tetrahedron:Asymmetry,1995,6(05):1063. |
| [6] | Kolb H C;Bennani Y L;Sharpless K B .[J].Tetrahedron:Asymmetry,1993,4(01):133. |
| [7] | Davies S G;Ichihara O .[J].Tetrahedron:Asymmetry,1996,7(07):1919. |
| [8] | Jiang B;Liu J-F;Zhao S-Y .[J].Organic Letters,2001,3(25):4011. |
| [9] | Karanewsky D S;Badia M C;Ciosek C P Jr;Robl J A, Sofia M J, Simpkins L M, DeLange B, Harrity T W, Biller S A, Gordon E M .[J].Journal of Medicinal Chemistry,1990,33(11):2952. |
| [10] | Kita K;Kataoka M;Shimizu S .[J].Journal of Bioscience and Bioengineering,1999,88(06):591. |
| [11] | Dahl AC.;Madsen JO. .Baker's yeast: production of D- and L-3-hydroxy esters[J].Tetrahedron, Asymmetry: The International Journal for Repid Publication on all Aspects of Asymmetry in Orgainc, Inorganic, Organometallic, Physical and Bio-Organic Chemistry,1998(24):4395-4417. |
| [12] | 何成,许建和,刘幽燕,庄英萍.固定化酵母非水相催化羰基不对称还原反应的研究[J].化学研究与应用,2001(06):632-635. |
| [13] | Zhou B-N;Gopalan A S;VanMiddlesworth F;Shien W-R, Sih C J .[J].Journal of the American Chemical Society,1983,105(18):5925. |
| [14] | 蒋群 .[D].杭州:浙江大学,2002. |
| [15] | Nakamura K;Kawai Y;Nakajima N;Ohno A .[J].Journal of Organic Chemistry,1991,56(15):4778. |
| [16] | Windholz M;Buhavari S;Blumetti R F.The Merck Index.10th Ed[M].Rahway:Merck & Co Inc,1983:909. |
| [17] | Nakamura K;Kondo S I;Kawai Y;Ohno A .[J].Tetrahedron Letters,1991,32(48):7075. |
上一张
下一张
上一张
下一张
计量
- 下载量()
- 访问量()
文章评分
- 您的评分：
-
10%
-
20%
-
30%
-
40%
-
50%